Process for treating hydrocarbons



A. B. CULBERTSON, JR

PROCESS FOR TREATING HYDROCARBONS Nov. 16, 1937.

Filed March e, 1935 Patented Nov. 1.6, 1937 UNITED STATES PATENT OFFICErnodnss mi mima mnoclnnows l'cadtafit tii Applicatie?4 iii, (lsiiznl)No. 9,577 Y d" Y This invention relates to treating hydrocarbons, andmore particularly to a process for blowing petroleum residues to produceblown asphalts and the like, and is a continuation in part of mygication Serial No. 403,895, led October 31,

VAli object of the invention is to provide an improved process forvblowing petroleum residue with air or other oxidizing gas fortransforming o the base material; for example, to produce a downflow`pipes II to the next lower tray and is blown asphalt from a residuumobtained in the withdrawn from the column through a pipe I1 distillationof an asphaltic base petroleum oil. The air or any other oxidizing gasis admitted Another object oi the invention is to provide a to thecolumn through anair conduit I2, having continuous process whereby acharging stock of a a pump 2B and a check` valve I4. An air flowselected type may be subjected to an intimate meter I6 is connected tothe'air line'so that 15 contact with air or other oxygen-containing gasthe volume of air entering the reaction chamber and whereby thecomposition of air and material may be measured. I have often found itadvan treated as well as the reaction temperature may tageous to injectair into column 1 at different be conveniently controlled. levels, whichprovides a more flexible control of Dimculties have heretofore beenexperienced, the oxidizingreaction taking place in the column 20 whenblowing petroleum oil residues, in properthan is attainable with the airinjection only at ly regulating the reaction to produce a conone point.Therefore, the air line I2 is provided trolled end product, and insecuring a uniform with a plurality of branch conduits I3 eachhavmixture of the air and material treated. The ing a valve I5, servingto control-separately the v methods primarily employed heretofore may beamount of air admitted to the column 1 by each 25 characterized as batchprocesses, as distinbranch. The oxidizing gas rises within thecolguished from continuous" processes. umn through the bubble caps IIa,in countercur- A,It has been discovered that a successful conrent flowto the stream of 4material under treattinuous blowing of materials ofthe kind menment descending through the overilow pipes yI I.

tioned` above may be accomplished and a uniform l Inorder to provide asensitive means of con- 30 product may be obtained by passing thematerials trol, I recirculate the withdrawn material, or acountercurrent to a stream of oxidizing gas, part thereof, through thereaction chamber by through a reaction chamber provided with means meansof a pump I8 and a pipe I9, after blending for separating the stream Voftreated `material so it, if desired, with fresh asphalt basel materialas to expose a relatively large surface for contact admitted throughpipes 3` l.and 6. Due tov the 35 withthe oxidizing gas, and-bycontrolling the ad-v exothermal reaction taking place within thecolmission of the gas to providea selected ratio of umn 1, the recycledoxidized asphalt imayhave a the volume of the reacting gas with thematerial y suflicient .heat` content `to make, the use rof the` treated.Furthermore, by controlling the comheater Ii superfluous,v inwhichfcase'the'raw oil 40 position and the amount o! the oxidizing gas,the "is conducted through conduits 3, I,y and 6,'thus by- 40 dangeroiexplosions may be eliminated and the `passing(tl'iejtubular heater I'.Furthermeansfor, ltemperature maintained during reaction maybe n.controlling thetemperature ofthe recycled matekept within practicallimits, l f, rial lnuiyfbe providedby using 'a'heating or cooll Theinvention will .further be understoodfrom ingeyheatexchangerr34 in therecycle line Illgff AIn the following description of a preferred form ofthis.- manr'1`er, 'the heat` rcontent o f the asphaltic 45`-.,apparat`usin which it-may be practiced.'1'h`ismateriali.toQbeloxidlzed can be accurately a'd-l .apparatus is`illustrated diagrammatically and 'I'j'sted'and the danger 'cfcaiising'either-overoxiv'partly incross-s'ectlononthe `drawing attached.,'datyiojn or'insmclent oxidation withinlthe'colunin it includes aconventional tube heater ,I1 having 1, can'be avoided; 'f' i",

lcoils;Lsupplied with the chargingv stock delivered Anadditionalmeanso'f; controlling temperatures 50 ,from a.V supply line 3. f f within`the reac onchamber'may. be provided'v in y Q'Iheheated stream of'pthecharging stock isv ftl'ieforrn,foi"fcoils'y` l3,5;*withinfth'e'c'.)lurri1'vk """of conducted throughthe' transfer line '8 tonearf thewhich nlyV oneisshownon the4 drawing, although l, top of the reactionchamber I through'acheck iany number f"sucl1'"`coils maybe used betw'erpreferably the plates ci the column. By circulating a 56 valve l, thetransfer line being equipped with a temperature recorder 9 forregistering the transfer temperature.

"The reaction chamber I comprises a column of suitable dimensions,containing a series of plates Ill provided with downiiow pipes II andbubblecaps Ila. The heatedstream of oil entering the top of the columngradually descends therethrough by gravity, forming a separate pool ofliquid on every tray before it overows through cooling or `a heatingmedium in these coils, and by automatically regulating the rate of ow oisaid medium by means of thermostatic control means 31, responsive to thetemperatures within the column, it is possible to keep the temperatureof the oxidizing reaction within desired limits. It is preferable thatthe coils 35 be installed in the vapor space between the plates of thecolumn, since in that case there is, less tendency for an asphalticcoating to `form on coils 35' and thus impair the rate of heat transfer.

Several relief valves 20, which serve as safety that this' process maybe particularly'advantageously used as a part of my `new method ofproducing blown asphalt. For this purpose, steam is admitted through aline 30, which enters the column at a point near its bottom and is pro-A' vi'dedwith a portion 38 preferably consisting of a yperforated pipe.The steam introduced by means of the pipe 38 into the bottom of thecolumn passes through the oxidized material accumulated therein, andlthen ascends through the column countercurrently tov and in contactwith the of the oxidizing gas, the asphaltic material in thelowerportion of the reaction chamber 1 is subjected vonly to the reducingaction of the steam, and this portion of the chamber may be consideredas a reducing section, while the upper portion of the chamber; whereinthe material under treatment is in contact with both the oxidizing gasand the steam, may be considered as an oxidizing section. If desired,steam may also be injected into th reaction chamber at various selectedlevelsl for which purpose the line 33 is provided with manifold branches32. The amount of steam injected at each point may be individuallycontrolled by .means oi valves 33. In this way, by controlling theamounts of steam and oxidizing gas injected at various points into thecolumn, it is possible to obtain a nal product of any desiredspecification with regard, for example, to viscosity,A

in chamber 40 may be stripped with steam or any stream. The bottomproduct obtained in the side colum'n M may be removed to storage throughpipe V43, or,1as a further means of controlling its desiredspecification, maybe recycled through the side column dihby means' ofpipe, connected to pipe 39, through which the stream of partly oxidizedmaterial from the main column 1 is admitted into vside column 40. Valvedpipe 39 between its juncture with pipe yM and its point of entry intoside column 40 may suitably contain a pump, not shown. Although only onecolumn is shown on the drawing, any number of such lside columns may beused iny combination with vthe main column. .f

The gaseous mixture within the column, con' sisting of residualoxidizing gas, oil vapors and steam, if the latter had been injectedinto the column, is withdrawn from the column by means of a vapor line2| leading outof the top of the reaction chamber to a condenser 22, towhich a. cooling mediumis supplied at a desired rate. This condenser maybe used to condense only the easily condensable, high-boilinghydrocarbons vapcrized from the asphaltic mixture by the heat of thereaction in column 1, in which case both the residual air and the steamissue from the condenser in gaseous form and may be recirculated throughthe column 1 by means of pipe 26 and air pump 28, after their heatcontent has been adjusted, if desired, by passing, them through a heatexchanger 3E, and fresh oxidizing gases have been added by means of pipeI2. It is also possible to condense both the hydrocarbon vapors andsteam in condenser 22, after which only the -partly exhausted oxidizinggas is recirculated through the system, as described above. Thecondensed portion of the gaseous phase withdrawn from column 1 isremoved from the condenser and may be directed to a separator (notshown) Where the oily material is separated from water; at least a partof the condensed oily material may be combined with the recycled oil inthe conduits I 9 or 6.

It will be understood that the charging stock to the main reactionchamber may, comprise either a residuum from topped crude petroleum oilsof asphalti base or a suitable cracked residue, or otherasphalt-producing material, such as coal-tar, coal-tar residue, etc. Thecharging stream is brought to a desirable temperature in the heater Iand then transferred from the heater to the reaction chamber undersuchconditions as to provide a suitable initial temperature for theblowing reaction in the reaction chamber. This initial temperature, ofcourse, lis

subject to variations depending upon the charging stock and the endproduct desired. With the usual charging stock the normal initialreaction temperature is approximately 425 F., the operating temperaturebeing Awithin the range 425-600 F.

The reaction is exothermic and, therefore, the temperature maintained inthe reaction chamber depends, to a substantial degree, upon the ratio ofthe volume of air orgas admitted to the reaction chamber to thevolume ofmaterial undergoing treatment. The final product is also iniluenced to aconsiderable degree by the extent of oxidation and the rapidity of thereaction. By providing means for controlling with accuracy the admissionof the oxidizing gas and by controlling the location of the points of.injectionv of the oxidizing gas to the reaction chamber, the reactionmay be kept under accurate control.

Furthermore, by exposing a large surface of the y material undertreatment, a very intimate con# tact between the pools of material vonseparate trays kand the oxidizing agent is accomplished.

I claim as my invention:

1. The p rocess of .blowing petroleum base ma- I-terials comprisingintroducing a stream of material to be treated at an elevation in areaction chamber, separating the stream into pools, said pools having` agravity downward flow, and passing separate currents of air at selectedelevations into the reaction chamber.

2. A continuous process of .producing blown asphalt which consists inpreheating a stream of base. material, 'causing a gravity flow of saidstream in a closed chamber in such manner as to separate the stream intopools, introducing for contact with said material currents of-air ofcon- -trolled volume whereby the temperature within the chamber iscontrolled, said air being intro,- duced at different elevations inrespctof the downward moving column of the material under treatment, andcontinuously withdrawing the.

asphaltic material after treatment.

3. The process of blowing petroleum base ma- 'terials comprisingintroducing a stream of material to be treated at anelevation in-areaction chamber, separating ,the stream into pools, said.

pools having a gravity downward ilow, passing separate currents of airat selected elevations into, the reaction chamber and causing the airthus introduced to pass through said pools in succession incountercurrent to the stream of material being treated. v e

4. A process of blowing asphalt-producing petroleum base materialsYcomprising, introducing a-` stream of material to be treated at anelevation `into a` reaction chamber, separating 'the stream -flow,injecting separate currents of an oxidizing gas at selected elevationsinto the reaction chamber, withdrawing the residual gases from thereaction chamber, withdrawing the oxidized petroleum base material fromthe reaction chamber and recirculating at least a. portion thereofthrough the reaction chamber.

6. A process of blowing asphalt-producing petroleum base materialscomprising, introducing a stream ofi material to be treated at anelevation into Aa reaction chamber, separating the stream into pools,said pools having a gravity downward ow, injecting'separate currents ofan oxidizing gas at selected elevations into the reaction chamber,withdrawing the residual gases from the,v re,

a'ction chamber and recirculating at least a portion thereof throughsaid chamber, withdrawing the oxidized petroleum base material from thereaction chamber and recirculating at least a portion thereof throughthe' reaction chamber.w

4FI. A continuous process of producing blown asphalt which consists inpreheating a stream of asphalt-producing petroleum base material,causing a gravity flow of said stream` in a reaction chamber in suchmanner as to separate the stream into pools,'introducing for contactwith Said material currentsof an oxidizing gas at different elevationswith respect to the downward moving column of the material undertreatment,

continuously withdrawing the oxidized petroleum base material from thereaction chamber, removing a portion thereof from the system, adjustingthe heat content of the remaining portion and recirculating it throughthe reaction chamber.

8. In the process of claim '7, the step of adjustthe heat content of theoxidized asphalt-producing material withdrawn from the reaction chamberby commingling it with fresh petroleum base material before returning itto the reaction chamber.

9. In the process of claim 7, the step of adjusting the heat content ofthe oxidized asphaltproducing material Withdrawn from the reactionchamber by commingling it with fresh cold petroleum base materialbefore'returning it to the reaction chamber.

l0. A process for blowing asphalt-producing petroleum base materialscomprising, introducing a stream of the material at an elevation intoV areaction chamber comprising an upper or oxidizing sectionv and a loweror reducing section, separating the stream into pools, said pools havinga gravity downward flow, passing a current of steam without oxidizinggas through the pools within the reducing section and continuing thesaid current of steam mixed with the oxidizing gas through the poolsWithin the oxidizing section.

11. A continuous process for blowing petroleum base materials whichconsists in introducing a stream of material to be treated at anelevation into a reaction chamber, separating the stream into pools,said pools having a gravity downward ilow, continuously introducing' acurrent of an oxidizing gas and a current of steam into said chamberin aplurality of separate streams at selected elevations for contact withthe material under treatment, withdrawing residual gases, steam andcondensable hydrocarbon vapors resulting from the reaction andVconducting them through a condensing zone wherein at least a portion ofsaid vapors is condensed and continuously withdrawing from the reactionchamber the oxidized petroleum base material.

12. A process for blowing asphalt-producing petroleum base materials,comprising introducing a stream of the material at an elevation into asteam and vaporized materials from the second reaction chamber into therst reaction chamber,

continuing the downward flow of the remaining portion of the material inthe rst reaction chamber to the bottom thereof, introducing a' currentof steam near the 'bottom of the first reaction chamber'below the pointof introduction of the oxidizing gas, and withdrawing the blown'materialfrom the bottom of the first reaction chamber. l

13. A process for blowing asphalt-producing petroleum base materials,comprising, introducing'a stream of the material at an elevation into a.reaction chamber, separating the stream into l. pools, said pools havinga gravity downward ow,

passing a current of oxidizing gas couritercurr'ent to the materialbeing treated, withdrawing a part of said material intermediate the topand the bottom of the reaction chamber, encuctmg the withdrawn portionto a second reaction chamber and steam-strlpp1ng it therein, continuingthe downward ow of the remaining portion oi' I thematerial in the firstchamber to the bottom thereof, withdrawing the blown material from thebottom of the iirst chamber and recirculatfing at least a portionthereof to the r'st chamber.

14. A process for blowing asphalt-producing petroleum base materials,comprising, introducinga. stream of` the material at. an elevation intoa reaction chamber, separating the stream ,into pools, said pools havinga gravity downward iiow, passing a current of oxidizing gascountereurrent top Y of the .tethe material being treated, withdrawing apart of said material intermediate the top and the bottpm'of thereaction'chamber, conducting the withdrawn portion to a second reactionchamber and steam-stripping it therein, recycling 'at least a'ncrtlon ofthe stripped material from a 1ow trom-the bottom of therst4 .reactionchamber and recycling at least a portion thereof to a highpoint intherst reaction chamber. i y" B. CULBERTSON, JR.

DISCLAIMER 2,099,434.3-Albert B. C'ulbertson, Jr., St. Louis, Mo. fPaocEes'FoR TREATING HYDRO- CARBONS. Patent .dated November'l, 1937,Disclaimer filed June 16,

1938, by the assgignee, Standard Oil Company (Indflkim). Hereby-enters'ths disclaimer to, but onlyrtoQ those claims in saidspecification which a'renumbered 4, 5, 6, 7,8, andr9. [Oficial GazetteJuly 12, 1938.]

the bottom of the reaction chamber, encuctmg the withdrawn portion to asecond reaction chamber and steam-strlpp1ng it therein, continuing thedownward ow of the remaining portion oi' I thematerial in the firstchamber to the bottom thereof, withdrawing the blown material from thebottom of the iirst chamber and recirculatfing at least a portionthereof to the r'st chamber.

14. A process for blowing asphalt-producing petroleum base materials,comprising, introducinga. stream of` the material at. an elevation intoa reaction chamber, separating the stream ,into pools, said pools havinga gravity downward iiow, passing a current of oxidizing gascountereurrent top Y of the .tethe material being treated, withdrawing apart of said material intermediate the top and the bottpm'of thereaction'chamber, conducting the withdrawn portion to a second reactionchamber and steam-stripping it therein, recycling 'at least a'ncrtlon ofthe stripped material from a 1ow trom-the bottom of therst4 .reactionchamber and recycling at least a portion thereof to a highpoint intherst reaction chamber. i y" B. CULBERTSON, JR.

DISCLAIMER 2,099,434.3-Albert B. C'ulbertson, Jr., St. Louis, Mo. fPaocEes'FoR TREATING HYDRO- CARBONS. Patent .dated November'l, 1937,Disclaimer filed June 16,

1938, by the assgignee, Standard Oil Company (Indflkim). Hereby-enters'ths disclaimer to, but onlyrtoQ those claims in saidspecification which a'renumbered 4, 5, 6, 7,8, andr9. [Oficial GazetteJuly 12, 1938.]

